Crude oil hydrorefining process



United States Patent 3,252,894 CRUDE OIL HYDRGREFiNlNG PROCESS John G.Gatsis, Des Plaines, and Wiiiiam K. T. Gieim, Island Lake, 111.,assignors to Universal Oil Products Company, Des Plaines, 111., acorporation of Delaware No Drawing. Filed Oct. 14, 1963, Ser. No,316,109 11 Claims. (Cl. 208-264) The present application is acontinuation-in-part of our copending application, Serial Number207,072, filed July 2, 1962, now abandoned, which copending applicationis incorporated herein by specific reference thereto.

The present invention relates to a method for preparing a novel catalystparticularly adaptable for utilization in the hydrorefining of petroleumcrude oils, heavy vacuum gas oils, heavy cycle stocks, crude oilresiduum, topped crude oils, etc. More specifically, the presentinvention involves a process for hydrorefining petroleum crude oil andother heavy hydrocarbon charge stocks to effect the removal of nitrogenand sulfur therefrom, and affords unexpected advantages in thedestructive removal of organo-metallic contaminants and/ or theconversion of pentane-insoluble hydrocarbonaceous material.

Petroleum crude oil, and the heavier hydrocarbon fractions and/ordistillates obtained therefrom, particularly heavy vacuum gas oils andtopped crudes, generally contain nitrogenous and sulfurous compounds inlarge quantities. In addition, petroleum crude oils containdetrimentally excessive quantities of organo-metallic contaminants whichexert deleterious effects upon the catalyst utilized in variousprocesses to which the crude oil, topped crude oil, or heavy hydrocarbonfraction may be ultimately subjected. The more common of such metalliccontaminants are nickel and vanadium, often existing in concentrationsin excess of 50 p.p.m., although other metals including iron, copper,etc., may be present. These metals exist within the petroleum crude oilin a variety of forms: they may exist as metal oxides or as sulfides,introduced into the crude oil as a form of metallic scale; they may bepresent in the form of soluble salts of such metals; usually, however,they are present in the form of organo-metallic compounds such as metalporphyrins and various derivatives thereof. Although the metalliccontaminants, existing as oxide or sulfide scale, may be removed, atleast in part, by a relatively, simple filtering technique, and thewater-soluble salts are at least in part removable, by washing and asubsequent dehydration procedure, a much more severe treatment isrequired to effect the destructive removal of the organo-mctalliccompounds, particularly to the degree necessary to produce a crude oilor heavy hydrocarbon fraction which is suitable for further processing.

In addition to organo-metallic contaminants, including metal porphyrins,crude oils contain greater quantities of sulfurous and nitrogenouscompounds than are generally found in lighter hydrocarbon fractions suchas gasoline, kerosene, light gas oil, etc. For example, a Wyoming sourcrude, having a gravity of 232 API at 60 F., contains about 2.8% byweight of sulfur and approximately 2700 ppm. of total nitrogen,calculated as the elements. The nitrogenous and sulfurous compounds areconverted, upon being subjected to a catalytic hydrorefining process,into hydrocarbons, ammonia and hydrogen sulfide. However, the reductionin the concentration of the organometallic contaminants is not easilyachieved, and to the extent that the same no longer exert a detrimentalelfect, particularly in regard to further processing of the crude oil.Notwithstanding that the total concentration of these metalliccontaminants may be relatively small, for example, less than about ppm.of metal porphyrins, calculated as the elemental metals, subsequentprocessing ice techniques will be adversely affected thereby. Thus, whena hydrocarbon charge stock containing metallic contaminants in excess ofabout 3.0 p.p.m., is subjected to a cracking process for the purpose ofproducing lowerboiling components, the metals become deposited upon thecatalyst employed, steadily increasing in quantity until such time asthe composition of the catalytic composite is changed to the extent thatundesirable results are obtained. That is to say, the composition of thecracking catalyst is closely controlled with respect to the nature ofthe charge stock being processed and to the desired product quality andquantity. This composition is changed considerably as a result of thedeposition of the metallic contaminants thereupon, the changed compositeresulting inherently in changed catalytic characteristics. Such anefiect is undesirable with respect to the cracking process, since thedeposition of metallic contaminants upon the catalyst results in alesser quantity of valuable liquid product, as well as large amounts ofhydrogen and coke, the latter also resulting in relatively rapidcatalyst deactivation.

In addition to the foregoing described contaminating influences, crudeoils and other heavier hydrocarbon fractions contain excessivequantities of pentane-insoluble material. For example, the Wyoming sourcrude described above consists of about 8.3% by weight ofpentame-insoluble asphaltenes; these are hydrocarbonaceous compoundsconsidered to be coke-precursors having the tendency to becomeimmediately deposited within the re action zone and onto the catalyticcomposite in the form of a high molecular weight, gummy residue. Sincethis constitutes a large loss of charge stock, it is economicallydesirable to convert such asphaltenes into useful hydrocarbon oilfractions, thereby increasing the liquid yield of desired product, basedupon the quantity of oil charged to the process.

The object of the present invention is to provide a much more efficientprocess for hydrorefining heavier hydrocar bonaceous material, andparticularly petroleum crude oil, utilizing an unsupported catalystprepared in a particular manner. The term hydrorefining, as employedherein, connotes the catalytic treatment, in an atmosphere of hydrogen,of a hydrocarbon fraction or distillate for the purpose of eliminatingand/ or reducing the concentration of the various contaminatinginfluences previously described. As hereinabove set forth, metals aregenerally removed from the charge stock by deposition of the same ontothe catalyst employed. This increases the amount of catalyst, activelyshields the catalytically active surfaces and centers from the materialbeing processed, and thereby generally precludes the utilization of afixed-bed catalyst system for processing such contaminated crude oil.Various moving-bed processes, employing catalytically active metalsdeposited upon a carrier material consisting, for example, of silicaand/or alumina, or other refractory inorganic ox de material, areextremely erosive, causing plant maintenance to become difiicult andexpensive. The present invention teaches the preparation of acolloidally dispersed, unsupported catalytic material useful in a slurryprocess, which catalytic material will not effect extensive erosion orcorrosion of the reaction system. The present process yields a liquidhydrocarbon product which is more suitable for further processingwithout experiencing the difiiculties otherwise resulting from thepresence of the foregoing contaminants. The process of the presentinvention is particularly advantageous for effecting the conversion ofthe organo-metallic contaminants without significant product yield loss,while simultaneously converting pentane-insoluble material intopentane-soluble liquid bydrocarbons.

In copending application, Serial Number 207,072, we have described anunsupported, colloidally dispersed catalytic material particularlyadaptable for slurry-type processing or" heavy oil fractions. Theunsupported catalyst is a decomposed heteropoly acid selected from themetals of Group VIB of the periodic table having an atomic numbergreater than 24. We have now found that significantly improved resultsare afforded when the hydrorefining reactions are effected in thepresence of hydrogen sulfide, added prior to initiating any of thehydrorefining reactions.

Therefore, a broad embodiment of the present invention involves aprocess for hydrorefining a hydrocarbon charge stock, which processcomprises admixing said charge stock with at least one heteropoly acidselected from the metals of Group Vl-B having an atomic number greaterthan 24, heating the resulting mixture to decompose said heteropolyacid, reacting the resulting colloidal suspension with hydrogen in thepresence of added hydrogen sulfide at a temperature above about 225 C.and at a pressure greater than about 500 pounds per square inch gauge,and recovering a hydrorefined liquid product.

A specific embodiment of the present invention encompasses a process forhydrorefining a petroleum crude oil containing pentane-insolubleasphaltenes, which process comprises admixing said crude oil withphosphomolybdic acid and an alcohol containing less than about elevencarbon atoms, heating the resulting mixture at a temperature below about310 C. and for a time sufiicient to decompose said phosphomolybdic acidand to remove the solvent alcohol, reacting the resulting colloidalsuspension with hydrogen in the presence of added hydrogen sulfide at atemperature within the range of from about 225? C. to about 500 C. andat a pressure of from about 500 to about 5000 pounds per square inchgauge, and recovering said crude oil substantially free frompentaneinsoluble asphaltenes.

From the foregoing embodiments, it is noted that the method of thepresent invention involves the preparation of a catalyst utilizingmetals selected from Group .VIB of the periodic table. Reference isherein made to the Periodic Chart of the Elements, pages 448 and 449,43rd edition of Handbook of Chemistry and Physics. It is further noted,that the metals from Group VI-B, namely molybdenum and/or tungsten, havean atomic number greater than 24. It has been found that heteropolyacids of chromium, in addition to other chromium complexes,

upon decomposition within the hydrocarbon charge stock, do not yieldcomparable results, and particularly with respect to the conversion ofthe pentane-insoluble fraction and the organo-metallic compoundsincluding nickel and/ or vanadium porphyrins. Furthermore, thedecomposition of chromium complexes is eflected above about 310 C.,resulting in premature cracking of the crude oil. Briefly, the catalystis preferably prepared by dissolving heteropoly molybdic acids and/ orheteropoly tungstic acids, such as phosphomolybdic acid, silicomolybdicacid, phosphotungstic acid, arsenomolybdic acid, and antimonomolybdicacid and silicotungstic acid in an appropriate solvent such as alcoholscontaining up to and including ten carbon atoms per molecule. Thesolution is added to the petroleum crude oil and the mixture distilledwith stirring, at a temperature less than about 310 C., to remove thesolvent and decompose the heteropoly acid, thereby creating acolloidally dispersed catalyst suspended within the petroleum crude oil.The quantity of the heteropoly acid employed is such that the colloidalsuspension, or dispersion, which results when the acid is decomposedwithin the hydrocarbon charge stock, comrises from about 1.0% to about10.0% by weight, calculated, however, as the elemental metal.

Suitable heteropoly acids, selected from the metals of Group VI-B havingan atomic number greater than 24, include phosphomolybdic,phosphotungstic acid, silico molybdic acid, silicotungstic acid, andmixtures thereof including phosphomolybdic acid-phosphotungstic acid,etc. The process is efiected, as hereinafter set forth in specificexamples, by initially dissolving the desired quantity of the heteropolyacid, such as phosphomolybdic acid, in the hydrocarbon charge stock.Although the use of the phosphomolybdic acid, as is, in a finely dividedstate does effect a significant degree of removal of sulfurouscompounds, reduces the concentration of the nickel and vanadiumporphyrins, and converts approximately of the pentane-insolubleasphaltenes into pentane-soluble hydrocarbons, the concentration ofnitrogenous compounds continues to be considerably high, and furthertreatment would appear to be indicated. However, when phosphomolybdicacid is dissolved in water, prior to the addition thereto of thepetroleum crude oil, the concentration of nitrogenous compounds issignificantly decreased, in addition to a more effective removal of theother contaminating influences. When the phosphomolybdic acid isinitially dissolved in an alcohol containing up to and including aboutten carbon atoms per molecule, in ketones, esters, etc., thecontaminating influences within the petroleum crude oil are removed tothe extent that the future processing of such crude oil no longerinvolves consideration of-the detrimental eifects otherwise resultingfrom the presence of large quantities of the contaminating influences.Typical of the alcohols suitable for use in preparing the solution ofthe desired heteropoly acid include isopropyl alcohol, isopentylalcohol, methyl alcohol, amyl alcohol, mixtures thereof, etc. Themixture of the alcohol solution of phosphomolybdic acid and thepetroleum crude oil is heated at a temperature below about 310 C. forthe purpose of distilling the alcohol, leaving the phosphomolybdic acidas a decomposed colloidal dispersion within the crude oil. Temperaturesabove about 310 C. tend to result in premature cracking reactionswhereby the effectiveness of the process to convert pentane-insolubleasphaltenes becomes adversely affected. The colloidal dispersion is thenpassed into a suitable reaciton zone maintained at a temperature withinthe range of from about 225 C. to about 500 C. and under a hydrogenpressure within the range of about 500 to about 500 pounds per squareinch gauge. The process may be conducted as a batch-type procedure or inan enclosed vessel through which the colloidal suspension is passed;when effected in a continuous manner, the process may be conducted ineither upward flow or downward flow. The normally liquid hydrocarbonsare separated from the total reaction zone eflluent by any suitablemeans, for example, through the use of a centrifuge or settling tanks,at least a portion of the resulting catalyst-containing sludge beingcombined with fresh petroleum crude oil, and recycled to the reactionzone. In order to maintain the highest possible degree of catalyticactivity, it is preferred that at least a portion of thecatalyst-containing sludge be removed from the process prior tocombining the remainder with fresh crude oil. The precise quantity ofthe catalyst-containing sludge removed from the process will bedependentupon the desired degree of contaminant removal. However, it is furtherdesirable to add a quantity of fresh phosphomolybdic acid to thepetroleum crude oil in order to compensate for that quantity ofmolybdenum, calculated as the elemental metal, removed from thecatalyst-containing sludge.

The colloidal dispersion of decomposed phosphomolybdic acid and crudeoil is reacted with hydrogen under the operating conditions aforesaid,and in the presence of added hydrogen sulfide. When dispersed in thecrude oil, the phosphomolybdic acid, or other heteropoly acid, appearsto be reduced to form a crystalline structure as yet unidentified. Assuch, the catalyst is capable of hydrogenating, and/or hydrocracking,the more easily reduced sulfur compounds in the crude oil, therebyproducing hydrogen sulfide. However, when the reactions are initiated inthe presence of added hydrogen sulfide a more active form of catalyst isproduced im-.

mediately, which form of catalyst is capableof the destructive removalof the less easily reduced sulfur compounds. As hereinafter indicated byspecific example, the more active form of catalyst is also capable of agreater degree of nitrogenous compound removal, yields a hydrorefinedproduct effluent containing lesser quantitles of metallic contaminantsand effects the conversion of a greater portion of the pentane-insolublefraction. Since this more active form of catalyst appears to have thesame crystalline structure, also not identified, as the catalyst used inthe absence of added hydrogen sulfide, the precise physical and/orchemical change effected therein is not known with accuracy. In aspecific example, an atmosphere completely devoid of hydrogen andconsisting solely of hydrogen sulfide caused the concentration ofsulfurous compounds to increase from 2.8% to 3.4% by weight, while onlyreducing the nitrogen concentration from 2700 p.p.m. to about 1800p.p.m. Thus, it may be surmised that the beneficial effects of the addedhydrogen sulfide occur only when the latter is present at the time thehydrogenation is being initiated; the hydrogen sulfide is added in anamount of from 1.0 to about 15.0 mol percent.

The following examples are given to illustrate the present invention,and to indicate the effectiveness thereof in hydrorefining a petroleumcrude oil to remove the various contaminating influences. It is notintended to limit the present invention to the catalyst, concentrationsof material, charge stock and/or conditions of operation.

The crude oil employed to illustrate the benefits afforded through theutilization of the present invention, was a Wyoming sour crude oilhaving a gravity of 232 API at 60 F., containing about 2.8% by weight ofsulfur, approximately 2700 p.p.m. of nitrogen, 18 p.p.m. of nickel and81 p.p.m. of vanadium as metal porphyrins, computed as the.elementalmetal. In addition, the sour crude consisted of about 8.3% by weight ofpentaneinsoluble asphaltenes. As hereinafter indicated, the process ofthe present invention not only effects the conversion of-a significantproportion of the pentane-insoluble asphaltenes, but also results in asubstantial production of lower-boiling hydrocarbons as indicated by anincrease in the gravity, API at 60 F., of the normally liquidhydrocarbon portion of the total product effluent.

Example I Phosphomolybdic acid, in an amount of 6.34 grams, as receivedfrom the manufacturer thereof, and without further treatment, was addedto 200 grams of the Wyoming sour crude. The mixture was placed in an 850cc. rocker-type autoclave, pressured to 100 atmospheres with hydrogen,and the temperature increased to a level of 400 C., resulting in apressure of 205 atmospheres. These conditions were maintained for aperiod of 12 hours, and the normally liquid hydrocarbon portion of thetotal product efiluent, following centrifugal separation, indicated 1790p.p.m. of nitrogen, 0.86% by weight of sulfur, 2.50% by weight ofpentane-insoluble asphaltenes, 6.0 p.p.m. of nickel and 3.0 p.p.m. ofvanadium.

The normally liquid hydrocarbon portion indicated a.

gravity, API at 60 F., of 29.8.

Sufficient phosphomolybdic acid, to provide 2.4% by weight of molybdenumin admixture wit-h 200 grams of the Wyoming sour crude, was ground to afinely-divided powder and added to the crude. The mixture was distilledto remove the fraction of the crude oil boiling within the normalgasoline boiling range, and thereafter placed within the rockerautoclave at a temperature of 400 C., resulting in a pressure of 191atmospheres of hydrogen, for a period of about 8 hours. The analysis ofthe normally liquid hydrocarbon portion of the total product efiluentindicated at least partial improvement over the results obtained whenthe phosphomolybdic acid was employed as received. The concentration ofExample I] In order to illustrate the substantial improvement resultingwhen the phosphomolybdic acid is added to the crude oil in solution, asufiic ient amount of phosphomolybdic acid (to yield 2.3% molybdenum)was dissolved in 150 grams of isopropyl alcohol. The solution was addeddropwise to 100 grams of the Wyoming sour crude, the mixture beingheated at a temperature of 120 C., thereby distilling off the alcohol asthe solution of phosphomolybdic acid was added. Upon complete additionof the solution, the sample was distilled to remove the normally liquidhydrocarbons boiling within the gasoline boiling range. The colloidalsuspension was placed Within the rocker autoclave, pressured to 100atmospheres with hydrogen and heated to a temperature of 400 C.,resulting in a pressure of 212 atmospheres. These conditions prevailedfor a period of 8 hours. Following a centrifugal separation from thecatalyst-containing sludge, the normally liquid hydrocarbon portion ofthe product efiluent indicated 309 p.p.m. of nitrogen, 0.23% by weightof sulfur, 0.09% by weight of pentaneinsoluble asphaltenes, 0.03 p.p.m.of nickel and 0.20 p.p.m. of vanadium. The normally liquid hydrocarbonportion also indicated a gravity, API at F., of 32.8. It will be noted,notwithstanding the relatively high degree of nitrogenous compoundsremaining in the normally liquid portion of the product effluent, thatthere has been a substantial improvement with respect to thecontaminating influence exhibited by sulfur, the asphaltenes, and thenickel and vanadium porphyrins. Furthermore, the increase in gravity,."API at 60 F., from 23.2 to about 32.8, indicates a significant degreeof conversion to lower-boiling hydrocarbon components.

Example III Phosphomolybdic acid, in an amount of 12.68 grams, wasdissolved in 300 grams of isopropyl alcohol over a steam bath. Thesolution was added to 500 grams of the sour Wyoming crude dropwise andwith stirring; the mixture was subjected to distillation, during thedropwise addition of the phosphomolybdic acid solution, to remove theisopropyl alcohol, leaving the phosphomolybdic acid as a finely divided,colloidally dispersed material within the crude oil. Of the resultingcolloidal suspension, grams were charged to the rocker autoclave. Whileat room temperature, the autoclave was pressured to 3.0 atmospheres withhydrogen sulfide, then to 100 atmospheres with hydrogen. The temperaturewas raised to 400 C., resulting in a pressure of 206 atmospheres, whichconditions were maintained for'8 hours. The normally liquid producteffi-uent, having a gravity, API at 60 F., of 33.9, vfollowingcentrifugal separation from the catalyst-containing sludge indicated 232p.p.m. of nitrogen, 0.32% by weight of sulfur, 0.09% by Weight ofpentane-insoluble asphaltenes, 0.05 p.p.m. of nickel, the vanadiumconcentration being 0.06 p.p.m.

When the autoclave was pressured to 6. 0 atmospheres of hydrogensulfide, then to 100 atmospheres with hydrogen, the normally liquidhydrocarbon product effluent indicated 71 p.p.m. of nitrogen, 0.05% byweight of sulfur, 0.05% by weight of pentane-insoluble asphaltenes, lessthan 0.03 p.p.m. 'of nickel and less than 0.03 p.p.m. of vanadium, thegravity, API at 60 F. being With the autoclave pressured to 12.0atmospheres with hydrogen sulfide, then to 100 atmospheres withhydrogen, the liquid product effluent had a gravity of 34.0 API at 60F., and contained 113 p.p.m. of nitrogen, 0.05%

by weight of sulfur, 0.04% by weight of pentane-insolubles, 0.06 p.p.m.of nickel and less than 0.06 ppm. of vanadium.

This example indicates the improved results obtained when thephosphomolybdic acid is dispersed as an alcohol solution within thepetroleum crude oil, and the additional activity imparted to thecatalyst as a result of the added hydrogen sulfide.

The foregoing specification and examples indicate the method of thepresent invention, by which method the hydrorefining of severelycontaminated petroleum crude oils is efifected. The utilization ofheteropoly acids in the presence of added hydrogen sulfide has beenshown to result in a liquid hydrocarbon product suitable for furtherprocessing without the accompanying detrimental effects otherwiseresulting through the presence of the various contaminating influences.

We claim as our invention:

1. A process .for hydrorefining a hydrocarbon charge stock whichcomprises admixing said charge stock with at least one heteropoly acidof a metal of Group VI-B having an atomic number greater than 24,heating the resulting mixture at a temperature less than about 310 C.and for a time sufficient to decompose said heteropoly acid, reactingthe resulting colloidal suspension with hydrogen and added hydrogensulfide at a temperature above above 225 C. and at a pressure greaterthan about 500 pounds per square inch gauge, said reaction beinginitiated in the presence of the added hydrogen sulfide, and recoveringa hydrorefined liquid product.

2. The process of claim 1 further characterized in that said colloidalsuspension is reacted with hydrogen and hydrogen sulfide at atemperature within the range of from about 225 C. to about 500 C. andunder an imposed pressure of from about 500 to about 5000 pounds persquare inch gauge.

3. The process of claim 1 further characterized in that said heteropolyacid comprises phosp-homolybdic acid.

4. The process of claim 1 further characterized in that said heteropolyacid comprises phosphotungstic acid.

5. A process for hydrorefining a petroleum crude oil containingpentane-insoluble asphaltenes which comprises admixing said crude oilwith at least one heteropoly acid of a metal of Group VI-B having anatomic number greater than 24, heating the resulting mixture at atemperature less than about 310 C. and for a time sufficient todecompose said heteropoly acid, reacting the resulting colloidalsuspension with hydrogen and added hydrogen sulfide at a temperatureabove about 225 C. and at a pressure greater than about 500 pounds persquare inch gauge, said reaction being initiated in the presence of theadded hydrogen sulfide, and recovering said crude oil substantially freefrom pentane-insoluble asphaltenes.

6. The process of claim 5 further characterized in that said heteropolyacid comprises phosphomoly-bdic acid.

7. The process of claim 5 further characterized in that said heteropolyacid comprises phosphotungstic acid.

8. The process of claim 5 further characterized in that said heteropolyacid comprises silicornolybdic acid.

9. The process of claim 5 further characterized in that said heteropolyacid comprises silicotungstic acid.

'10. A process for hydrorefining a petroleum crude oil containingpentane-insoluble asphaltenes which comprises admixing said crude oilwith phosphornolybdic acid and an alcohol containing less than abouteleven carbon atoms, heating the resulting mixture at a temperature lessthan about 310 C. and for a time suificient to decompose saidphosphomoly'bdic acid, reacting the resulting colloidal suspension withhydrogen and added hydrogen sulfide at a temperature within the range ofabout 225 C. to about 500 C. and at a pressure of from about 500 toabout 5000 pounds per square inch guage, said reaction being initiatedin the presence of the added hydrogen sulfide, and recovering said crudeoil substantially free from pentane-insoluble asphaltenes.

11. The process of claim it) further characterized in that said hydrogensulfide is added in an amount within the range of from about 1.0 toabout 15.0 mol percent.

References Cited by the Examiner UNITED STATES PATENTS 2,554,597 5/1951Starnes et al 208213 DELB-ERT E. GANTZ, Primary Examiner.

S. P. JONES, Assistant Examiner.

1. A PROCESS FOR HYDROREFINING A HYDROCARBON CHARGE STOCK WHICHCOMPRISES ADMXING SAID CHARGE STOCK WITH AT LEAST ONE HETEROPOLY ACID OFA MEAL OF GROUP VI-B HAVING AN ATOMIC NUMBER GREATER THAN 24, HEATINGTHE RESULTING MIXTURE AT A TEMPERATURE LESS THAN ABOUT 310*C. AND FOR ATIME SUFFICIENT TO DECOMPOSE SAID HETEROPOLY ACID, REACTING THERESULTING COLLOIDAL SUSPENSION WITH HYDROGEN AND ADDED HYDROGEN SULFIDEAT A TEMPERATURE ABOVE ABOVE 225*C. AND AT A PRESSURE GREATER THAN ABOUT500 POUNDS PER SQUARE INCH GAUGE, SAID REACTION BEING INITIATED IN THEPRESENCE OF THE ADDED HYDROGEN SULFIDE, AND RECOVERING A HYDROREFINEDLIQUID PRODUCT.